Light-sensitive material having developers embedded therein

ABSTRACT

Light-sensitive photographic material having reducible metal compound that forms metal nuclei when exposed to light, and also has reducing agent incorporated in it to form an image when processed without an external developer, shows greater storage stability when the reducing agent is selected from certain hydroxy chromans and coumaranes. The reducible metal compound can be a compound of silver or other Group Ib metal, and can be formed in situ from a non-light sensitive silver salt.

United States Patent [191 Von Kiinig et a1,

[11] 3,819,382 .luneZS, 1974 LIGHT-SENSITIVE MATERIAL HAVING DEVELOPERS EMBEDDED THERETN Inventors: Anita Von Kiinig, Leverkusen;

Helmut Kampler; Ernst Roos, both of Cologne; Kurt Ley, Leverkusen, all of Germany Agfa-Gevaert Aktiengesellschaft,

Assignee:

Leverkusen, Germany Filed: June 23, 1971 App1.No.: 156,047

Foreign Application Priority Data June 26, 1970 Germany 2031748 US. Cl 96/1141, 117/368, 117/369, 96/95 UX Int. Cl. G036 l/02 Field of Search 96/114.1; 117/368, 36.2, 117/369 References Cited UNITED STATES PATENTS 9/1964 Baumann et a1 117/369 3,166,433 1/1965 Baumann et a1. 117/369 3,167,444 l/l965 Baumann et 117/369 3,185,585 5/1965 Baumann et al..... 117/369 3,330,663 7/1967 Weyde et a1 96/1143 3,457,075 7/1969 Morgan et a1. 96/1 14.1 3,463,655 8/1969 lmamiya et a1. 117/362 Primary Examiner-Ronald H. Smith Assistant Examiner-M. F. Kelly Attorney, Agent, or FirmConnolly and Hutz [5 7] ABSTRACT 3 Claims, N0 Drawings LIGHT-SENSITIVE MATERIAL HAVING DEVELOPERS EMBEDDED 3-: a l N The principle of embedding developer substances in photographic emulsion layers has been known for a long time but the substances conventionally used for this purpose, which are based on aromatic compounds substituted with hydroxyl or amino groups, do not satisfy all the requirements in practice. Some of these compounds do not have a sufficiently powerful development action, whereas those which are sufficiently powerful developers diminish the stability in storage of the light-sensitive layers. The reason for this is the sensitivity of the developers to oxidation with atmospheric oxygen.

The photographic processes for processing exposed, light-sensitive materials which contain embedded developer substances may be subdivided into two main groups, one group comprising those processes in which aqueous treatment baths are used, whereas the other group comprises processes in which the exposed photographic materials are processed at elevated temperature without the use of development baths.

In the first group of processes, the materials are developed simply by the action of an alkaline solution and are stabilized against further changes by light by means of stabilizer baths or by fixing and washing with water.

" The heat copying processes belong to the second group.

The principle of heat copying processes has been described in German Patent Specification, No. 880,045 and involves developing the material by simply heating it after exposure. The process described in German Patent Specification No. 1,300,014 also belongs to the heat copying type of process. In the process described in the last-mentioned patent specification, photographic recording materials are used which contain an oxidizing agent, a reducing agent and a minorquantity of a light-sensitive substance whose photolytic products initiate the redox reaction which is accompanied by production of color. The oxidizing agents used in this process are organic silver salts and the reducing agents are aminophenols, hydroxylamines, pyrazolidones or phenols. Phenylene diamine and etherified naphthols e.g. 4-methoxynaphtholl, have also been described as reducing agents for this purpose. Compounds suitable for use as light-sensitive compounds are heavy metal salts which form traces of the free metal on exposure to light, especially light-sensitive silver salts such as silver halides which form silver by a photolytic reaction on exposure to light. These photolytic heavy metal nuclei initiate the redox reaction. 7

The materials used in the said process also have the above mentioned disadvantage of being relatively unstable in storage due to the sensitivity of the reducing agents to oxidation by atmospheric oxygen. To obtain sufficient stability in storage for practical requirements, it is, therefore, necessary to take additional steps to protect the reducing agents against the action of atmospheric oxygen. This is achieved mainly by the addition of antioxidants.

It is among the present objects of the invention to provide a photographic material which contains silver salt and embedded developer substance suitable for wet or dry development processes, which developers should have a sufficiently powerful development action and sufficient resistance to oxidation in order to enable photographic images of high quality to be produced from a material of sufficient stability in storage.

It has now been found that compounds of the following general formula are eminently suitable developer substances or reducing agents for this purpose:

R1 R2 Rn C n R5 R1 R4 11 Rs Rs wherein n 0 or 1;

R R R R R and R hydrogen or alkyl groups having up to 9 carbon atoms, preferably methyl groups;

R and R or R and R may be joined together to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms which can contain a double bond and/or which can be substituted by alkyl groups having up to 4 carbon atoms;

R, may further stand for an alkoxy group having up to 6 carbon atoms or a tertiary amino group of the following formula:

. wherein R and R represent alkyl having up to 6 carbon atoms or are together the ring members required for completing a S-membered, 6-membered or 7- membered ring which may contain an oxygen atom or a nitrogen atom as ring member in addition to the nitrogen atom already present;

R and R hydrogen, alkyl or alkoxy having up to 6 carbon atoms, preferably methyl or tertiary alkyl groups, and, at least one of them represents a by droxyl group;

R and R hydrogen, alkyl or alkoxy having up to 9 carbon atoms, preferably methyl or tertiary alkyl groups, cycloalkyl such as cyclopentyl or cyclohexyl, aralkyl such as benzyl or phenyl ethyl, or aryl, especially a phenyl ring, or a group of the formula:

wherein R and R have the meanings already indicated. The following are examples of suitable compounds:

I) 2-methyl-6-hydroxy-chroman,

2) 2,2-dimethyl-6-hydroxy-chroman,

3) 2,2,3-trimethyl-6-hydroxy-chroman,

4) 2,2 dimethyl-7-tert-butyl-6-hydroxy-chroman, 5) 2,2-dimethyl-8-tert-butyl-6-hydroxy-chroman,

ethyl)-6-hydroxyethy1)-6- l8) 2-dimethylamino-3 ,3-dimethyl-5-hydroxycoumaran, 19) 2-diethylamino-3,3-dimethyl-5-hydroxycoumaran,

20) 2-pyrrolidino-3,3-dimethyl-5-hydroxy-coumaran, 21 2-piperidino-3,3-dimethyl-5-hydroxy-coumaran, 22) 2-morpholino-3,3-dimethyl-5-hydroxy-coumaran, 23) 2-morpholino-3,3-dimethyl-6-tert-butyl-5- hydroxy-coumaran,

24) 2-pyrrolidino-3,3-dimethyl-6-tert-butyl-5-hydroxycoumaran,

25) 2-piperidino-3,3-dimethy1-6-tert-butyl-5-hydroxycoumaran,

26) 2-morpholino-3,3-dimethyl-6-tert-octyl-5- hydroxy-coumaran,

27) 2-morpholino,-3,3-dimethyl-6-phenyl-5-hydroxycoumaran,

28) 2-pyrrolidino-3,3-(spiro-cyclohexen-(3)-yl)-5- hydroxy-coumaran,

29) 2-morpholino-3,3-(spiro-cyclohexyl)-5-hydroxycoumaran,

30) 2-piperidino-3,3-(spiro-cyclohexen-(3)-yl)-5- hydroxy-coumaran,

3 l 2-morpholino-3,3-( Spiro-3 '-methyl-cyclohexen- (3)-yl)-5-hydroxy-coumaran,

32) 2-morpholino-3,3-dimethyl-6-morpholino-methyl- 5-hydroxy-coumaran,

33) 2-morpholino-3,3-(spiro-4-methyl-cyclohexen- (3 )-yl )-5-hydroxy-coumaran,

34) 2-morpholino-3,3-(spiro-4'-methyl-cyclohexen- (3)-yl)-6-morpholino-methyl-5-hydroxy-coumaran, 35) 2-morpholino-2,3-tetramethylene-S-hydroxycoumaran,

36) 2,2-dimethyl-7-hydroxy-coumaran,

37) 2,Z-dimethyl-6-tert-butyl-7-hydroxy-coumaran, 38) 2-methoxy-3,3-dimethyl-5-hydroxy-coumaran, 39) 2-methoxy-3,3-dimethyl-6-tert-octyl-5-hydroxycoumaran,

40) 2-ethoxy-3,3-dimethyl-5-hydroxy-coumaran,

41) 2-methoxy-3,3-(spiro-4-methyl-cyclohexen-( 3')- yl)-5-hydroxy-coumaran,

42) 2-n-butyloxy-3,3-dimethyl-6-tert-butyl-5-hydroxycoumaran,

43) compound of the constitution:

I The process preparingqhe compounds to be used according to the invention is known and has been described inter alia in U.S. Pat. No. 3,160,637 and in German Patent Specification No. 1,163,837.

The photographic materials according to the invention which contain one or more of the foregoing developer substances are not in principle subject to any restrictions as regards their photographic application. They may be used wherever light-sensitive materials which contain developer substances are required. They may be used both for wet and for dry processing methods.

The optimum developer substances for any given photographic process can be selected by means of simple tests.

The materials according to the invention may contain both silver halides and organic silver salts, e.g. the silver salts of carboxyalkylthio derivatives or silver salts of carboxylic acids as described in British Patent Specification Nos. 1,11 1,492 and 1,110,046 or mixtures of these silver salts. These silver salts are sufficiently lightsensitive if precipitated in the presence of a protective colloid such as gelatin.

Any silver halide emulsions may be used for producing the silver halide emulsion layers, such as silver chloride, silver bromide or silver chlorobromide emulsions, and they may also contain up to 10 mols percent of silver iodide. These emulsions may contain 0.05 to 0.5 mol of silver halide per litre. For wet processing and for thermal development, the layers may contain the organic silver salts of carboxyalkylthio derivatives described in British Patent Specification No. 1,111,492 instead of silver halides or in admixture with silver halides.

The binder used for the photographic layers is preferably gelatin but this may be partly or completely replaced by other natural or synthetic binders. Suitable natural binders are, e.g. alginic acid and its derivatives such as salts, esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or its derivatives such as ethers or esters or carrageenates. Suitable synthetic binders are, e.g. polyvinyl alcohol, partially saponified polyvinyl acetate or polyvinyl pyrrolidone andthe lilce.

The binder mixtures of gelatin and cellulose acetate described in German Auslegeschrift No. 2,000,926 may also be used, the gelatin solution for the layer being in that case mixed in the presence of phthalic acid in quantities of 10 to 50 percent by weight, based on the total amount of solids in the mixture, with cellulose acetate having an acetic acid content of between 30 and 50 percent by weight. The emulsions may also be chemically sensitized, e.g. by adding compounds which contain sulfur, such as allyl isothiocyanate, allyl thiourea or sodium thiosulfate and the like, at the stage of chemical ripening. Reducing agents may also be used as chemical sensitizers, e.g. the tin compounds described in Belgian Patent No. 493,464 and 568,687,

polyamines such as diethylene triamine or formamidine sulfinic acid derivatives, e.g. according to Belgian Patent No. 547,323.

The emulsions may also be sensitized with polyalkylene oxide derivatives, e.g. with polyethylene oxide having a molecular weight of between 1000 and 20,000, with condensation products of alkylene oxides and the aliphatic alcohols, glycols or cyclic dehydration products of hexitols or with alkyl substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700 and preferably more than 1000. These sensitizers may, of course, be combined in order to achieve special effects, as described in BelgianPatent No.'537,278 and in British Patent Specification No. 727,982.

The emulsions may also be spectrally sensitized, e.g. with the usual polymethine dyes such as merocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes or oxonoles. Sensitizers of this type have been described in the work by F. M. Hamer The Cyanine Dyes and Related Compounds (1964).

The'emulsions may contain the usual stabilizers, e.g. homopolar or salt-type compounds of mercury which have aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Azaindenes are also suitable for use as stabilizers, especially tetraor penta-azaindenes and especially those which are substituted with hydroxyl or amino groups.

Compounds of this type have been described in the article by Birr, Z. Wiss. Phot. 47, 2 58(1952). Other suitable stabilizers are e.g. heterocyclic mercapto compounds such as phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazoles or the substituted 4-aminobenzotriazoles described in British Patent No. 919,061.

The emulsions may be hardened for wet processing in the usual manner, for example with formaldehyde or halo-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters or dialdehydes.

When using the light-sensitive materials according to the invention for heat copying processes, it is advisable also to add other substances, for example matting agents such as starch ether, dextrin, colloidal silicic acid or finely dispersed silicon dioxide, aluminum oxide or titanium dioxide. For some heat copying processes it has been found especially advantageous to add substances which impart a certain moisture to the lightsensitive layer and/or the image receiving layer during the heat development. This group of substances includes substances which split off water at elevated temperature or hydrophilic compounds which increase the residual moisture of the layer. Substances of the first mentioned type are ureas, caprolactam, B-nitroethanols or B-cyanoethanols as described in German Patent Specification No. 1,174,159 or salts which form clearly defined hydrates, such as sodium acetate, sodium citrate or sodium sulfate. Compounds of the second type mentioned include glycols, polyethylene glycols, glycerol, sorbitol' or mono or oligo-saccharides. These substances are added to the casting solutions for the light-sensitive layer in such quantities that the dry layer contains about 0.1 to g/m of these substances.

. The light-sensitive layer may be arranged on any layer support such as paper, synthetic resin, fabric or layer support must be stable at the usual temperatures employed.

In certain cases, it is advantageous to interpose an intermediate layer between the support and the emulsion layer. Intermediate layers of this type which are suitable for development at elevated temperature have been described e.g. in German Patent Specification N 0. 1,189,383.

The developer substances to be used according to the invention may be added to the emulsion layers which contain silver salts or to the intermediate layers in amounts of 50 to 1000 g, preferably to 700 g, per mol of silver salt.

These photographic materials can be developed simply by the action of an alkaline solution after exposure to light and are, therefore, suitable both for use as negative rnaterial for the silver salt diffusion process and as copying material for processing in the two-bath process and for conventional processing by fixing and washing.

When the developer substances to be used according to the invention have been embedded in the photographic layer, they are differentiated from known developer substances such as hydroquinone, aminophenol or p-methylaminophenol etc. by their improved resistance to oxidation. Furthermore, the photographic materials produced with these developer substances have less fog.

The compounds to be used according to the invention and the photographic materials containing them are especially suitable for a heat copying process of the following type.

A photographic recording material for the production of copies by the dry process contains as oxidizing agent a silver salt which is substantially insensitive to light, a reducing agent and a light-sensitive heavy metal compound which on exposure forms metal nuclei by photolysis, thus initiating the redox reaction on heating, the reducing agent used being one or more of the compounds according to the invention represented by the general formula indicated, which compounds are capableof reducing the light-sensitive silver salt at temperatures of between 50C and C in the presence of the photolytically produced heavy metal nuclei.

Suitable oxidizing agents of the image-producing redox system are silver salts of organic acids which, under the conditions of the process, are either insensitive to light or sensitive to light only to a negligible extent, e.g. silver saccharide, silver 5-chlorosalicylic aldoxime, silver 5-nitrosalicylic aldoxime or, preferably, a silver salt of a long chained fatty acid having up to 30 carbon atoms, e.g. silver stearate, silver palmitate or silver behenate or the silver salts of aliphatic carboxylic acids containing a thioether group as described in US. Patent No. 3,330,663. Silver salts of the last mentioned kind are light-insensitive if prepared in the absence of protective colloids such as gelatin.

The light-insensitive silver salt serving as oxidizing agent generally is used in a molar ratio of between 1:1 and 1:10 with respect to the above-defined reducing agent.

Suitable light-sensitive heavy metal salts which when exposed to light form metal nuclei capable of initiating the image-producing redox reaction are e.g. inorganic or organic salts of silver, mercury or gold. The heavy metals of the sub-group lb of the Periodic System of Elements are preferred, especially silver salts and among these again the silver halides.

The most suitable light-sensitive heavy metal salts for any given redox system can easily be determined by a few simple laboratory tests. Thus, for example, the metal salt may be mixed with the components of the redox reaction in the form of its aqueous suspension. If it is to be suitable, it must not undergo any change in the dark but when the mixture is exposed to UV light, it should undergo discoloration within a few seconds. If both these conditions are fulfilled, the heavy metal salt is suitable for the redox system.

The light-sensitive heavy metal salt is used in comparatively small quantities of about 0.05 to 0.2 percent by weight, based on the weight of the oxidizing agent. This proportion of light-sensitive salt is sufficient in most cases but a higher or lower percentage may, of course, also be used.

The light-sensitive heavy metal salt, e.g. silver halide, should be present in such small quantities that the photolytically produced heavy metal nuclei are capable of initiating the redox reaction, but at the same time the concentration of the silver halide is so low that the metal nuclei formed do not cause any discoloration of the copying material, or only to a negligible extent.

The silver halide may be added to the casting solution for the layer which contains the components of the redox reaction or it may be formed in situ in the casting solution, e.g. by precipitation of the silver halide in the mixture. The silver ions for the precipitated silver halide may in that case be derived mainly from the silver salt which is not light-sensitive.

The silver salts which are not light-sensitive and which are present as oxidizing agents may be obtained in a known manner exactly like the silver halide by precipitation of silver salt solutions, e.g. by the precipitation of silver nitrate with the alkali metal salts ofthe organic acids preferably in the absence of protective colloids. The free acid may, of course, be present during precipitation but, in order to obtain highly transparent layers, it is advantageous to have only a slight excess of free acid present or even to use stoichiometric quantities of the organic acid and the silver salt.

Various methods may be used for preparing silver halides from the light-insensitive silver salts. For example, the surface of the light-insensitive silver salts may be treated with vapors of hydrohalic acids, e.g. hydrochloric acid, hydrobromic acid or hydriodic acid. The quantity of silver halide produced on the surface may be kept within the required limits by adjusting the concentration of the hydrogen halide in the vapor phase and the treatment time.

The light-insensitive silver salts of the organic acids may, of course, also be treated with a solution containing halogen ions, such as chloride ions, bromide ions or iodide ions. These halogen ions may be obtained from the hydrohalic acids themselves or from their salts, in particular their ammonium, alkali metal, or alkaline earth metal salts.

The reaction of the light-insensitive silver salts with the compounds which give off halogen ions is preferably carried out with the silver salts in the form ofa suspension in a volatile, non-aqueous liquid, although also the dry salts may be reacted, for example with hydrogen halide vapors.

In addition to hydrohalic acids and their salts, e. g. the alkali metal salts, ammonium salts and alkaline earth metal salts already mentioned above and other metal salts, e.g. zinc salts and mercury salts, there may also be used for formation of the light-sensitive silver halides ionisable organic halogen compounds, e.g. triphenylmethyl chloride, triphenylmethyl bromide, 2- bromo-2-methyl propane, 2-bromo-butyric acid, 2- bromoethanol or benzophenone dichloride.

The materials according to this embodiment of the invention are preferably prepared by formation of the light-sensitive silver halides from the'light-insensitive silver salts of the organic acids. This enhances the capacity of the silver halides to produce photolytic silver nuclei which are especially effective in initiating the redox reaction. Although useful materials can also be obtained by preparing the silver halides separately and subsequently mixing them with the light-insensitive silver salts, the photolytic heavy metal nuclei formed from such mixtures are generally not so active.

To prepare the material according to the invention, the components for the redox reaction and the lightsensitive heavy metal are used together with a suitable binder. The binders used are preferably organic polymers such as copolymers of vinyl chloride and vinyl acetate or of butadiene and styrene, polyethylene, polyamides, polyisobutylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl pyrrolidone, polystyrene, chlorinated rubber, polyvinyl butyral, polymers of acrylic acid or methacrylic acid esters or copolymers of the derivatives of acrylic acid and methacrylic acid, cellulose derivatives such as nitro cellulose, cellulose acetates, cellulose propionates or mixtures thereof such as cellulose acetobutyrates.

The light-sensitive layer may be used as a selfsupporting layer but it-is preferably applied to a suitable layer support. The layer support must be stable at the processing temperatures of between 60C and 200C. Suitable supports are e.g. sheets or foils of paper, cellulose acetate, polyethylene terephthalate, textile fabrics, metal foils or glass. Where paper supports are used, the paper may contain the usual suxiliary layers such as baryta layers and/or polyethylene layers.

The concentration of the reducing agent and of the oxidizing agent in the layer may vary within wide limits.

Proportions by weight of 4:1 to about 1:1 between the components of the redox reaction and the binder have generally been found sufficient.

The thickness of the light-sensitive layer may also be adapted to the requirements of the given reproduction process. Layer thicknesses of between 5 and microns are generally sufficient for the usual requirements. The layer supports have the usual thicknesses of between about 0.1 and 0.8 mm.

Also in this embodiment of the invention the lightsensitive layers may be spectrally sensitized by the addition of dyes.

The usual white pigments such as silicon dioxide and toners such as phthalazone, phthalazone derivatives and phthalimide may be added to the light-sensitive layers.

The photographic materials according to the invention are processed in a known manner. Image-wise exposure is carried out with the usual light sources used in photographic work, e.g. mercury lamps, iodine quartz lamps or simple incandescent lamps. The type of light source used depends on the spectral sensitivity of the heavy metal salt. In the preferred method using silver halides, the usual incandescent lamps are sufficient. The exposure time is a few seconds.

The exposed material is then uniformly heated to a temperature of between about 60C and 160C. The time and temperature required for the heat treatment depends on the nature of the redox system. Periods of between 3 and 80 seconds are generally sufficient. A dark brown to black image is formed which is ready for immediate use.

Example 1 Light-sensitive material:

An equimolar mixture of silver behenate and behenic acid is prepared by precipitating silver nitrate with a solution of sodium behenate and behenic acid in alcohol and water. The precipitate is carefully washed and dried.

The suspension used for preparation of the layer is prepared by treating the mixture described below in a ball mill for 12 hours:

240 ml of methanol,

125 ml of a solution of polyvinyl-n-butyral in methanol,

ml of a 10% solution of poly-N-vinyl pyrrolidone in methanol,

g of an equimolar mixture of silver behenate and behenic acid,

10 ml of a 1% methanolic solution of ammonium bromide,

1.2 g of phthalazone, and

15 g of 2,2-dimethyl-7-tert-butyl-6-hydroxy-chroman (Compound 4).

The above mixture is applied to a conventional paper support at a concentration of 100 g/sq.m and dried at room temperature.

Processing:

The light-sensitive layer is exposed through a transparent original. The source of light used is a 750 Watt UV lamp at a distance of 5 cm. The exposure time is 2 seconds and the distance from the source of light 5 cm. The material is then heated to a temperature of 80C for 5 seconds.

A black-brown negative image of the original is obtained.

Similar results are obtained when using eg Compound 38 or Compound 24 instead of the compound described above.

Example 2 Light-sensitive material:

Suspension for bottom layer:

1.8 g of a mixture of silver behenate and behenic acid (molar ratio 1:1),

3 g of cellulose acetate,

3 g of phthalazone,

4.5 ml of calcium bromide solution (1 g dissolved in 100 ml of methanol),

5.7 ml of mercury-ll-acetate solution (1 g 1 ml of glacial acetic acid dissolved in 100 ml of methanol),

3 ml of a solution of 1-methyl-3-al1yl-5-[2-(3-ethylbenzoxazolylidene-( 2 )-ethylidene -2- thiohydantoin (0.01 g dissolved in 100 ml of chloroform),

0.15 g of silicon dioxide,

55 g of acetone,

1 g of copolymer of vinyl chloride and vinyl acetate 88: 12 dissolved in 20 g of butyl acetate. Top layer:

10 g of polyvinyl butyral,

1.5 g of phthalazone,

5 g of 2-methoxy-3,3-dimethyl-5-hydroxy coumaran (Compound 38),

ml of methanol.

The suspension for the bottom layer is ground in a ball mill for about 16 hours and then applied on baryta paper and dried. The silver application is 0.3 to 0.4 g/m The top layer is cast on thedry bottom layer. The amount of reducing agent applied is 0.5 to 1.5 g/m Instead of Compound 38, the following reducing agents may be added to the top layer:

6 g of Compound 23,

6 g of Compound 25,

4 g of Compound 36,

5 g of Compound 4, or

5 g of a mixture of Compounds 4 and 5.

The reducing agents may also be added to the suspension for the bottom layer instead of that for the top layer, and ground with this suspension in a ball mill for about one-half hour, e.g.:

8 g of Compound 43,

8 g of Compound 33.

Processing:

The light-sensitive material is exposed with tungsten lamps for 3 to 30 seconds depending on the intensity of the lamps and the required gradation, and developed by heat. The development time varies from 3 to 80 seconds according to the height of the temperature within the range of 60C to 160C and the apparatus used. The apparatus used for development may be heatable presses, drying drums, rollers or the apparatus described in Belgium Patent No. 628,174 or in French Patents Nos. 1,512,332; l,416,752 or 1,419,101 or the usual commercial apparatus. To protect the photographic layer and to produce a high gloss image, the layer surface of the material may be kept in contact with a polyester foil during the heat development.

The images obtained-on development are brown or brownish black to neutral black images on a white to yellow ground, depending on the developer substance used and the processing conditions.

Example 3 Light-sensitive material:

The following substances are added to 1 kg of a silver chloride gelatin emulsion which contains 0.2 mol of silver halide with a silver iodide content of .less than 0.1 mols 20 mg of l-phenyl-5-mercaptotetrazol (1% in alcohol),

g of sodium acetate (cryst.) (1:1 dissolved in water),

5 g of colloidal silicic acid,

20 g of Compound 4 or Compound 38 dissolved in methanol, and

5 ml of saponin (30% aqueous solution).

The pH of the emulsion is adjusted to 5.1 with sulfuric acid. The emulsion is applied on a baryta paper in a known manner and dried. Silver application 1.2 glm Processing:

After exposure the rear surface of the coated paper is placed in contact for 0.5 to 60 seconds with a metal or synthetic resin surface heated to 90 to 200C or with a liquid heat transfer agent. The apparatus used for development may be conventional heat development apparatus or heatable presses, drying drums, rollers or the apparatus described in Belgian Patent No. 628,174 or the image-wise exposed negative may be exposed to infra-red radiation for about 10 to 180 seconds.

A dark brown image is obtained.

The well-covered silver image has little sensitivity to light. It may be stabilized by fixing and washing in water or by bathing it in an alcoholic solution of 2,5-dimercaptol ,3 ,4-thiadiazole or l-phenyl-S- mercaptotetrazole.

Example 4 Light-sensitive material:

A paper is coated with a solution of:

100 g of the sodium salt of polyurea sulfonic acid prepared by polyaddition of the sodium salt of 4,4- diaminodiphenylethane-2,2"disulfonic acid with tolylene diisocyanate,

125 g of cane agar, and

2.5 litres of water.

After this coating is dried it is covered with a coating of the following silver halide gelatin emulsion:

1 kg of a silver chloride gelatin emulsion which contains, per kg of emulsion, 0.2 mol of silver halide with a silver iodide content of less than 0.1 mols 200 mg of 4-hydroxy-6-methyl-1,3,3a,7-

tetraazaindene (dissolved in alcohol), 50 mg of benzotriazole (dissolved in alcohol), 100 g of sodium acetate (cryst.) 1:1 dissolved in water), 20 g of Compound 23 or Compound 4 dissolved in methanol, 3 g of colloidal silicic acid, and ml of saponin (30% aqueous solution). The pH of the emulsion is adjusted to 4.9 with sulfuric acid. Silver application 1.2 g/m The material is exposed and processed as described in Example 3 and a brownish black image is obtained.

Example 5 The following substances are added to 1 kg of an unwashed silver chlorobromide gelatin emulsion which contains per kg 0.18 mol of silver halide (20 mols AgBr):

2.7 ml of a 40% citric acid solution,

30 mg of l-phenyl-5-mercaptotetrazole (1% in alcohol),

3 g of colloidal silicic acid and 1 litre of a solution of phthalic acid in methanol.

This emulsion is added with stirring to a solution of 3 litres of a 3 percent solution of a cellulose acetate (acetate group content 40 percent by weight) in acetone/- water (1:4) and 1 litre of a 10 percent solution of phthalic acid in methanol and 60 g of Compound 38 or 60 g of Compound 43, and the emulsion is then applied to a baryta paper. Silver application 1.2 g/m The material is exposed and processed as described in Example 3 and a brown image is obtained.

The exposed material may also be developed for 1 minute in 10 percent sodium hydroxide solution and fixed and washed in the usual manner. A black, wellcovered image is obtained.

Example 6 2 m1 of a 40 percent aqueous citric acid solution are added to 1 litre of a 10 percent aqueous gelatin solution, and the solution is heated to 40C. 22 g of 2-noctylthio-5-carboxymethylthio-1,3,4-thiadiazole dissolved in the equimolar quantity of sodium hydroxide solution are then added and the solution is precipitated with 100 ml of a 10 percent silver nitrate solution with vigorous stirring, and 1 litre of a 10 percent solution of phthalic acid in methanol is added with stirring. This emulsion is added with stirring to a solution of 2 litres of a 3 percent solution of a cellulose acetate (acetate group content 40 percent by weight) in acetone/water (4:1) and 200 ml of a 10 percent solution of phthalic acid in methanol and 50 g of Compound 38 or 50 g of Compound 25, and the emulsion is then applied to a layer support as in Example 3. Silver application 0.6 g/m If desired, 10.2 g of 3-carboxymethylthio-l,2,4- triazole may be used instead of 22 g of 2-n-octylthio-5- carboxymethylthio-l ,3,4-thiadiazole.

The material is processed as described in Example 3 and a brownish black image is obtained.

The exposed material may also be developed for 1 minute in a 10 percent sodium carbonate solution and fixed and washed in the usual manner. A black image is obtained.

Example 7 The following substances are added to 1 kg of a silver chloride gelatin emulsion which contains, per kg of emulsion, 0.2 mol of silver halide which has a silver iodide content of less than 0.1 mols percent:

2.7 ml of a 40% aqueous citric acid solution,

40 mg of 1-phenyl-S-mercaptotetrazole 1% in alcohol),

10 ml of a 30% formaldehyde solution,

25 ml of a 10% aqueous saponin solution, and

20 g of Compound 23, or

20 g of Compound 43 dissolved in methanol.

The emulsion is applied to baryta paper in a known manner and dried. Silver application 1.3 g/m The exposed material is developed in a 10 percent aqueous sodium carbonate solution for one minute and fixed and washed in the usual manner. A well-covered black image is obtained.

Example 8 The exposed material described in Example 7 may also be brought into contact with the image-receiving layer described hereinafter in a commercial apparatus conventionally used for the silver salt diffusion process, and developed in the following activator solution:

Anhydrous sodium sulfite 4 anhydrous sodium phosphate 3 sodium hydroxide sodium thiosulfate cryst. potassium bromide made up with water to The two layers are separated after a contact time of 15 to 30 seconds.

A black image with good whites is obtained. Image-receiving material:

A layer of baryta is applied from the follwing solution to a layer support of paoer g/m): 6 ml of a 50% aqueous suspension of barium sulfate,

20 ml of a 10% aqueous gelatin solution, 8 ml of a 50% aqueous emulsion of polyvinyl acetate,

water up to ml.

The baryta layer is dried and then coated with an image-receiving layer from the following casting solution:

4.5g of propylene glycol alginate, 12.5 mg of silver sulfide in the form of an aqueous colloidal solution, 20 ml of a 50% aqueous gelatin solution, 1.5 ml of a 30% aqueous solution of potassium bromide, 1.2 ml of a 30% aqueous solution of saponin, 7.5 g of sodium thiosulfate, made up with water'to 300 ml. The layer is applied in such a thickness that it contains about 1.1 g of sodium thiosulfate per m A layer of the following casting solution is then applied to the aforesaid image-receiving layer:

3.5 g of sodium alginate, g of sodium thiosulfate, 0.8 ml of a 30% aqueous potassium bromide solution, 8 ml of a 30% aqueous saponin solution, 0.5 ml of a l% alcoholic solution of 3-mercapto-4,5-

dimethyll ,2,4-triazole, made up with water to 350 ml! This layer is applied in such thickness that it contains about 0.6 g of sodium thiosulfate per m Example 9 A light-sensitive photographic material comprising a silver chloride gelatin emulsion layer on a support, which emulsion layer contains per kg of casting solution 0.2 mol of silver halide with less than 0.1 mol percent of silver iodide (silver application 1.3 g/m and Compound 38 or Compound 43 g/kg of emulsion) is exposed image-wise and developed in the following 7 activator solution in an ordinary'commercial two bath apparatus:

60 g of sodium hydroxide,

50 g of anhydrous sodium sulfite 2 g of potassium bromide,

made up with water to 1 litre.

The developed material is treated with the following stabilizer solution:

250 g of ammonium thiocyanate,

80 g of potassium metabisulfite,

20 ml of acetic acid, I

20 g of the sodium salt of the cyclohexanone bisulfite adduct,

made up with water to 1 litre.

A grey-black image with good whites is obtained.

If the above mentioned emulsion is mixed with phthalic acid and cellulose acetate as described in Example 5, a black image is obtained.

We claim: p

l. A light-sensitive photographic sheet material con taining a silver salt composition which comprises a light-insensitive silver salt, a catalytic amount of silver wherein n is 0 or 1;

R R R R R and R are hydrogen or alkyl groups having up to 9 carbon atoms, but

R and R, or R and R may be joined together to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms, and

R may further represent an alkoxy group having up to 6 carbon atoms or a tertiary amino group of the formula:

wherein R and R represent alkyl having up to 6 carbon atoms or are together the ring members required for completing a 5-, 6- or 7-membered ring;

R R are hydrogen, alkyl or alkoxy having up to 6 carbon atoms, and at least one of them represents a hydroxyl group;

R R are hydrogen, alkyl or alkoxy having up to 9 carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:

wherein R and R have the meanings indicated above.

2. A light-sensitive photographic sheet material containing 21 silver salt composition which comprises silver behenate reducible in the proximity of a catalytic amount of silver nuclei by weak reducing agents, and containing a reducing agent that causes development of a visible image by reducing the silver salt composition when processed with heat, wherein the improvement comprises the reducing agent has the following formula:

Ru R{ R:

R11 R; 0 Rs wherein n is 0 or 1;

halide, and containing a reducing agent that causes development of a visible image by reducing the silver salt V Rt R:

G in RI Br Ra Rn Rs 0 Re R R R R R and R are hydrogen or alkyl groups having up to 9 carbon atoms, but

R and R or R and R may be joined together to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms, and

R may further represent an alkoxy group having up to 6 carbon atoms or a tertiary amino group of the formula:

r V g 15 A I V 16 wherein V wherein R and R represent alkyl having up to 6 carbon n i r 1;

atoms or are together the ring members required R R R R R and R are hydrogen or alkyl groups for completing a 5-, 6- or 7-membered ring; h i up t 9 carb at ms, but R R are hydrogen, alkyl or alkoxy having up to 6 5 R3 d R or R d R may b j i d t th t carbon atoms, and at least one of them represents complete a b li i system havi g 5, 6 or a hydroxyl g P; I 7 carbon atoms, and 11 12 are hydrogen, alkyl or alkoxy havmg up to 9 R may further represent an alkoxy group having up carbon atoms, cycloalkyl, aralkyl, aryl or a group to 6 Carbon atoms or a tertiary amino group of the of the formula: 0 formula.

H CH:N 1

R 15 Ih wherein wherein R and R have the meanings indicated above.

3. A light-sensitive photographic sheet material containing a silver salt composition which comprises a light-insensitive silver salt of a fatty acid, a catalytic amount of silver nuclei, and containing a reducing agent that causes development of a visible image by reducing the silver salt composition when processed with a hydroxyl p; heat, wherein the improvement comprises the reducing 11 12 are hydrogeni alkyl or alkoxy havmg up to 9 agent h th f ll i f l carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:

R and R represent alkyl having up to 6 carbon atoms or are together the ring members required for completing a 5-, 6- or 7-membered ring;

R R are hydrogen, alkyl or alkoxy having up to 6 carbon atoms, and at least one of them represents C n R; R! 7 R1 R4 R1: R5 wherein 0 R. 5 R and R" have the meanings indicated above. 9 i k i 1 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 9, 3 Dat d June 25, 197' Inventor(s) Anita von Konig et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 56 compound ll should read 2-methoxy-3,3- (sp1ro- 1-methyl-cyclohexen-(3')- Column 9, line 63 should read benzoxazolyidene-(gl)- ethy1idene1-2- Signed and sealed this 8th day of April 1975.

' C. IL XPSHALL DANN RUTl-I I Commissioner of Patents and Trademarks FORM PC4050 (10-69) USCOMM-DC GOS'IB'PGQ U. 5. GOVERNMENT PRINTING OFFICE "I! O-J66-38l,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 9, 3 Dat d June 25, 197' Inventor(s) Anita von Konig et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 56 compound ll should read 2-methoxy-3,3- (sp1ro- 1-methyl-cyclohexen-(3')- Column 9, line 63 should read benzoxazolyidene-(gl)- ethy1idene1-2- Signed and sealed this 8th day of April 1975.

' C. IL XPSHALL DANN RUTl-I I Commissioner of Patents and Trademarks FORM PC4050 (10-69) USCOMM-DC GOS'IB'PGQ U. 5. GOVERNMENT PRINTING OFFICE "I! O-J66-38l, 

2. A light-sensitive photographic sheet material containing a silver salt composition which comprises silver behenate reducible in the proximity of a catalytic amount of silver nuclei by weak reducing agents, and containing a reducing agent that causes development of a visible image by reducing the silver salt composition when processed with heat, wherein the improvement comprises the reducing agent has the following formula:
 3. A light-sensitive photographic sheet material containing a silver salt composition which comprises a light-insensitive silver salt of a fatty acid, a catalytic amount of silver nuclei, and containing a reducing agent that causes development of a visible image by reducing the silver salt composition when processed with heat, wherein the improvement comprises the reducing agent has the following formula: 